Rubber impregnated fibrous material



Oct. 2%, 1937. s. a. NEILEY I 2,097,417

RUBBER IMPREGNATED FIBROUS MATERIAL Original Filed April 5, 1935 inve zior I Stephen B. Nei/ey y rm jjg g A flomey Patented Oct. 26, 1937 UNITED STATES PATENT OFFICE 2,091,411 RUBBER mirancmran ruinous MATE Stephen B. Neiley, Winchester, Masa, assignor to Dewey and Almy Chemical Company, North setxabridge, Mara, a corporation of Massachu- Orlglnal application April 5, 1935, Serial No. 14,734. Divided and this application December 12, 1935, Serial No.- 54,079 Y 2 Claims. (01. I 91-68) This is a division of my application, Serial 14,734, filed April 5, 1935. In the first filed application I am claiming the process by which the product is produced. In the present applicoagulant, such as set forth in my United States patent, Reissue #19,426 dated January 15, 1935, then impregnating a specially prepared, impregnant-receptive web therein, subsequently revers- 5 cation I am claiming the product itself. ing the capillary-active forces which normally 5 In the production of artificial leather made cause the rubber to concentrate at the surface from latex rubber impregnated fibrous mateand immediately thereafter-activating the corial, two difliculties are present. First, assumagulant by heat to cause the instant coagulation ing that the web is a proper base stock to reof the rubber latex throughout the web.

ceive impregnants and that the latex is so skill- I find that this produces a web with as high a 10 fully compounded as to impregnate the sheet rubber content as may be required, but having uniformly, both of which are known steps in afibrous, open surface. I the art, it still will be found that capillary active As I set forth in detail in my United States forces drag the rubber particles out towards the paten m ntio v a di v red tha f" surface as the latex dries and that the surface tain zinc complex ions which dissociate at teml5 portion of the sheet contains more rubber than peratures higher than normal atmospheric temdoes the interior. The concentration of'rubber peratures, but below the boiling pointgof water, may be sufficient to form what may approach a do not coagulate rubber latex until the tempera.-v continuous surface film. Pyroxylin, to use this ture of the composition is raised above a critic substance as a single example, bonds poorly to a value at which temperature free zinc cations are 20 continuous rubber surface, consequently, since released which cause coagulation, i a most artificial leather is now coated with Accordingly, in the latex bath, I place a supply pyroxylin finishes and grained, the bond of the of complex zinc cations (Zn(NI-Ia)4++) in the pyroxylin to the base stock is not secure. form of zinc-ammonium chloride, acetate, or

The second difficulty is that-the adhesion of benzoate as the patent sets forth. I 25 the coating may be increased by reducing the When the temperature of the whole web rises rubber content of the whole 'web, but since many to 140 F. to 178 Frdepending upon the particuof the desirable characteristics of the artificial lar salt and its concentration, the complex breaks leather are imparted by the rubber, this ordiup, releasing free zinc cations (Zn++) and narily, is a step in the wrong direction and proforthwith the latex in the web coagulates. 30 duces an inferior product.- i In my present process, the-heating is, however,

It is an object of this invention to secure the much more thoroughand more suddenly secured highest possible degree of adhesion of the coatthan my previous process contemplated or pracing; to produce-a coating receptive surface with- *ticed. I I l out relation to the rubber content of the web, I have determined that-the instant coagulation 35 and to permit rubber containing webs having brought about by the sudden release .ofiactive high rubber content to be used in coated ions throughout the mass produces a sheet which I products. These and other objects will become has greatly increased tear resistance and is pracapparent from the specification and from the tically free from ply separation. For example,

40 drawing in which if asheet of water-laidfelt or saturating paper 40 Figure l is a semi-schematic view showing the be impregnated with normal vulcanizable latex arrangement of one form .of apparatus for the dried and cured, the sheet will separate into plies practice of my invention. whentorn which correspond to the increments of Figure 2 is also asemi-schematic view and fiber added to the sheet by the paper-making illustrates an alternative form of apparatus. machine during manufacture. It is my belief 45 Figure 3 is an enlarged view, partially in secthat in the case of normal latex the rubber tion, showing my improved web, and therein is drawn against the individual fibersas Figure 4 is anenlarged view, partially in secthe sheet dries, collects at the intersections of tion showing the completed product, a coated the fibers and forms fillets about, and buttresses web. Y I to the fiber structure. On the other hand, how'- 5 I have discovered that it is possible toproduce ever, by following my process outlined above and a localized surface condition of low' rubber conincorporating an identical amount of rubber in tent having an open, fibrous structure into which the same web and then'causing the latexto cothe coating may penetrate and bond securely by agulate suddenly in situ before drying and it will be found that the sheet tears directly 55 employing first in the latex a heat dissociable through its whole body and shows no tendency to separate into plies.

It is known that as rubber latex coagulates, filamentary processes shoot out from the globule, which, meeting others, interlace and build up a reticulated mass. Accordingly, I believe that by my process a second network of rubber tendr'ils or fibers is built up within the sheet and that this structure is formed substantially without relation to the felt fibers of the web. At any event, however, a very definite reinforcing action occurs which cannot be attributed to the presence of rubber alone and which prevents the separation of the sheet into plies.

Due to the instantaneous coagulation of the rubber latex I find it possible to distribute the rubber non-uniformly throughout the sheet. This may be done by reversing the capillary-active forces, which normally cause the rubber to concentrate at the surface, and immediately thereafter causing coagulation to take place. Coagulated latex will not migrate. I may bring about a reversal of the capillary-active forces in a number of ways, but, preferably, a reversal may be brought about by saturating the surface with a mobile fiuid and so bringing about a higher concentration of liquid at the surface than exists throughout the remainder of the sheet.

' In Figure 1 a schematic showing of one machine used in my process, the web III is unrolled into the impregnating bath il in the tank l2. It passes under the anchor roll I! and between the adjustable squeeze rolls I4 and I I (the surplus material removing mechanisms are conventional and not shown). From there, the web passes into a hood li'in which are one or more transverse pipes "-11 which bear nozzles ll-ll arranged to throw a uniform spray over the surface 20 of the web. Directly beneath the nozzles are placed the rolls 19-49 which take the thrust of the spray and prevent the weak web from being punctured or torn. The web then passes to a conventional drier and reeling apparatus.

As taught in my United States patent to which I have referred, the latex bath ll contains in solution a complex salt, preferably zlnc ammonium chloride, acetate or benzoate (although for special purposes other complex salts may be used), the concentration ofthe zinc cations of which is about one third of one per cent of the total mass.

A water solution of the same salt at the same massconcentration is sprayed out through the nozzles l8-l8. The web now has its upper surface 20 drenched with this solution and not only is the latex in thesurface layer diluted but, I believe, the capillary-active forces are reversed and the latex is dragged thereby back into the web. There is, also, a scouring action due to the force of the solution itself. All these effects build up to produce a surface layer (2l', Fig. 3) of the web which is practically denuded of latex. Then, as the web passes onto the drier, it absorbs heat, the complex salt dissociates, releasing active cations both in the layer 2| and in the body portion 22 (Fig. 3) of the web and immediately the latex coagulates, leaving the surface 2| permanently quite rubber-free.

The drier heat. may be adjusted to cure the dried latex which is now non-uniformly distributed in the web if proper vulcanizing and accelerating ingredients have been added.

In an alternative procedure, which may be 11- lustrated by the medium (Figure 1), the

web I0 is unrolled into the impregnating bath II as before, but instead of forcing a water solution of a complex salt through the nozzles ll-ll,'I

now blow a jet of saturated steam through these and onto the latex impregnated web. The entrained water and condensate from the steam soak the surface layer. 2| cf the web as before and since heat is being carried into the web by the steam, coagulation starts more quickly. but after the latex has been dragged away from the surface layer. I have, in consequence, not found it essential to maintain the concentration of coagulant constantthroughout the mass, which is necessary when cool water is used.

The pressure of the steam, the amount of entrained water, the speed of the travelling web, and the concentration of the coagulant are all process variables which depend upon the absorptivity of theweb and the type of product one desires to produce. Accordingly, I give no definite values but state that with a definite end product in mind, they may easily be determined by experiment.

. Although I prefer to reduce the rubber content of the surface layer by means of the steam blast since I have found that this permits a more accurate process, I have produced a satisfactory sheet with a surface layer practically denuded of rubber without recourse to mechanical forces released from the steam blast or from the water spray. r

- Yet a third modification of myprocess is illustrated in Fig. 2. The web Ilia is unrolled into a latex bath Ha. which contains a "dormant coagulant of the same class as before. It passes under the anchor roll "a and between the squeeze-rolls Ila and Ila. From there it passes under the hood 16a and over a roll 22 which revalves in a tank 24 of hot zinc'ammonium chloride, acetate, or benzoate solution 2|. sure roll 26 insures the full contact of the web Illa. with the roll 2!.

The salt inthe solution 25 is the active coagulating product of the dormant coagulant. used in the latex bath Ha and its concentration is. of such an amount as will equal that of the coagulant when dissociated in'the latex. In this case, also, before coagulation occurs, a substantial quantity of latex has beenremoved from the sur-'- face.

Figure 3 shows, partially in cross sectionythe web in having a high rubber body portion 22 and a low rubber surface layer 2|.

Although the web is designed for coating and finds its greatest utility in this form, I desire to point out that coating is generally carried on as a separate business and that a web having a coat- .ing receptive surface is an article of commerce by itself.

, The finished product is illustrated in Fig. .4.-

In addition to the web ID, with its high rubber body portion 22, and its low rubber surface layer 2|, the sheet carries a coating 21 of pyroxylih,

The pres- 1. An impregnated sheet suitable for an artificial leather base consisting of a single fibrous web having a capillary absorptive structure, said web having a non-uniform distribution of rubber therein from surface to surface, the amount of rubber present at one surface of the sheet being substantially greater than at the opposite surface and the web being free from peeling, said surface of the web having a reduced rubber content, being open and the rubber being present in to that surface or amount to bind the fibres but not in sumcient amount to prevent adherence of a cottinl material the sheet, whereby to form a eoating receptive surface. 7

2. An impregnated sheet material in accordance with claim 1 having a coating material applied to the surface having a reduced rubber content and forming a continuous flim adhered to such surface.

- mm B. NEILEY. 

